Phosphonic acid ester fluorides and a process for their manufacture



PHOSPHONIC ACID ESTER FLUORIDES AND A PROCESS FOR THEIR MANUFACTUREHans-Joachim Tuppack, Leverlrusen, and Gerhard Schrader,Wuppertal-Cronenberg, Germany, assignors to Farbenfabriken BayerAktiengesellschaft, Leverkusen, Germany, a corporation of Germany NoDrawing. Filed May 28, 1958, Ser. No. 738,295 Claims priority,application Germany June 3, 1957 14 Claims. (Cl. 260-461) The presentinvention relates to and has as its objects new and useful insecticides.Generally these compounds may be represented by the following formula (son.

The above shown adducts of phosphorus pentachlon'de and fl-alkoxyorS-alkylmercapto-vinyl-ethers may also be reduced with hydrogen sulfideso as to form B-alkoxyor B-alkylmercapto-vinyl thionophosphonic aciddichlorides:

It has been found that these fi-alkoxyor-alkylmercapto-vinyl-phosphonicor -thionophosphonic acid dichlorides maybe converted with alkali metal fluorides in the presence of any alcoholinto the above shown hitherto unknown ,B-alkoxyor-alkylmercapto-vinyl-phosphonicor thionophosphonic acid ester fluoridesof the above formula.

The reaction is expediently carried out in the presence of an inertsolvent at temperatures of between 65 and 80 C. Particularly usefulsolvents are benzene, toluene and chlorobenzene. The alkalimetalfluoride should be finely divided and free of water.

The new compounds of the present invention very effectively kill insectslike flies, mites, aphids, etc. They States Patent 0? distinguishthemselves especially by a. good contactinsecticidal activity and at thesame time by an activity on eating insects such as caterpillars. Mostsurprisingly they are of remarkable low toxicity against mammals. Theymay be used in the same manner as other known phosphoric insecticides,ie in a concentration from about 0.00001% to about 1%, diluted orextended with suitable solid or liquid carriers or diluents. Examples ofsuch solid carriers are talc, chalk, bentonite, clay and the like, asliquid carriers there may be mentioned water (if necessary with acommercial emulsifier), alcohols, es-

, 2,962,517 Patented Nov. 29, 1960 pecially lower alcohols such asmethanol or ethanol, ketones, especially lower ketones such as acetoneor methyl ethyl ketone, liquid hydrocarbons and the like. The newcompounds may furthermore be 'used in combination with each other orwith known insecticides, fertilizers etc.

The insecticidal activity of the inventive compounds may be seen fromthe following test results.

Aqueous dilutions of the following compounds.

have been prepared by mixing the active ingredient with the same amountof dimethyl formamide as an auxiliary solvent, adding thereafter 20% byweight referred to active ingredient of a commercial emulsifierconsisting of a benzyl hydroxy polyglycol ether containing about 10 to15 glycol residues, and diluting at last this premixture with water tothe desired concentration indicated in the following paragraphs. Thetests have been carried out in the following manner:

Against flies of the type Musca domestica (with compounds (a) and (b)About 50 flies were placed under covered Petri dishes in which drip wetfilter paper has been placed which is sprayed with an insecticidalsolution as prepared above. The living status of the flies has beendetermined after 24 hours; solutions of 0.001% kill flies 100%;

Against aphids of the type Doralis fabae (contactinsecticidal action)(with compounds (b)). Heavily infested bean plants (Vitia faba) havebeen sprayed drip wet with solutions as prepared above. The effect hasbeen determined by. evaluation after 24 hours by counting the dead pestseither on the surface of the soil or still remaining on the plants;solutions of 0.01% kill aphids 100%.

Further, activities of the inventive compounds are to be found in thefollowing examples, which are given by way of illustration only without,however, limiting the present invention thereto:

Example 1 O OCzHs 85 grams of finely divided anhydrous sodium fluorideare dissolved in 200 millilitres of toluene. While stirring there areadded 20 grams of absolute ethyl ethanol. At C. there are added whilestirring 76 grams of 9- ethoxy vinyl phosphonic acid dichloride (HP. 1mm./ The temperature is kept for 1 hour at 80' to C. and the reactionmixture then is allowed to cool down. From impurities and precipitatedsalts the mixture is filtered with suction and the filtrate then isfreed from solvents by filtration in vacuum. The residual 13- ethoxyvinyl phosphonic' acid ethyl ester fluoride is distilled under 0.01mm./70 C. and there are obtained 45 grams (55% of the theoretically) ofthe new ester which is a pale water-insoluble oil. Toxicity on rats peros LD 25 mg./kg. Fliesarekilled completely with solutions of 0.001%,caterpillars are killed completely with solutions of 0.1%. ,Systemicaction. on aphidsiwith solutions of 0.l%=l00%.

By exactly the same way but using instead of'fl-ethoxy vinyl phosphonicacid dichloride the equimolecular amount of B-ethoxy vinylthiophosphonic acid dichloride there is obtained the ester of thefollowing formula 85 grams of sodium fluoride are suspended in 200millilitres of toluene. There are added while stirring 25 grams ofisopropanol and 1 drop of water. 76 grams of fi-ethoxy vinyl phosphonicacid dichloride are added dropwise with vigorous stirring at 80 C. Thereaction is exothermic. When the reaction has subsided, the product iswarmed to 90 C. for a further hour, then cooled to room temperature andthe filtrate is fractionated. 40 grams of B-ethoxy vinylfluorophosphonic acid isopropyl ester of B.P. 74 C./0.01 mm. Hg are thusobtained. Yield 50% of the theoretical. The new ester is a colorlessWater-insoluble oil which shows a mean toxicity on rats per os of 25milligrams per kilogram. Solutions of 0.01% kill grain weevils, Coloradobeetles and aphids 100%. Flies are killed completely with solutions of0.001%, and caterpillars are killed completely with 0.1% solutions.Systemic action on aphids with solutions of 0.1%=100%.

By exactly the same way but using instead of ,8- ethoxy-vinyl phosphonicacid dichloride the equimolecular amount of fi-ethyl mercapto vinylthiophosphonic acid there is obtained the ester of the following formulaO OCH:

210 grams of sodium fluoride are suspended in 500 millilitres of benzeneand 32 grams of methanol are added with stirring. 190 grams offi-ethoxyvinyl phosphonic acid dichloride are then added dropwisethereto at 65 C. and the mixture is kept at 65 C. for a further hour.After filtering off with suction from the salts, the product isdistilled. The new ester has a RP. 808l C./1 mm. Hg. Yield: 52 grams.The fl-ethoxyvinyl fluorophosphonic acid methylester is a pale yellowWaterinsoluble oil. Yield: 30% of the theoretical. The new ester has atoxicity on rats per es of 250 mg./kg. Grain weevils and aphids arekilled completely with solutions of 0.01%. Caterpillars are killedcompletely with solutions of 0.1%.

By the same way but using instead of fi-ethoxy vinyl phosphonic aciddichloride the equimolecular amount of ,B-ethyl mercapto vinylphosphonic acid dichloride there is obtained the ester of the followingformula 85 grams of sodium fluoride are suspended in 200 millilitres oftoluene. To this solution there are added 30 grams of secondary butylalcohol. Then there are added at C. while stirring 70 grams offl-methoxy vinyl phosphonic acid dichloride. The temperature is kept for1 further hour at 90 C., cooled down to room temperature and then thesalts are filtered off. While fractionation of the filtrate there areobtained 70 grams of the new ester fluoride of BF. 0.01 mm./80 C. Yield:81% of the theoretical. Toxicity on rats per os LD 25 mg./kg. Solutionsof 0.01% kill aphids and spider mites completely and solutions of 0.001%kill flies completely.

When using instead of fi-rnethoxy vinyl phosphonic acid dichloride theequimolecular amount of fi-methoxy vinyl thiophosphonic acid dichloridethere is obtained the ester of the following formula 85 grams of sodiumfluoride are suspended in 200 millilitres of toluene. Thereto are added41 grams of n-hexyl alcohol. Then there are added dropwise at 80 C. 76grams of fi-ethoxy vinyl phosphonic acid dichloride. The temperature iskept for 1 further hour at C. and the mixture is worked up in a usualmanner. There are obtained 63 grams of the new fluorophosphonic acidester of HP. 0.01 mm./96 C. Yield: 65% of the theoretical. Toxicity onrats per osmium 50 nag/kg. LD Solutions of 0.01% kill aphids and spidermites completely. Caterpillars are killed completely with 0.1% solution.

Example 6 85 grams of sodium fluoride are suspended in 200 millilitresof toluene. Thereto are added 34 grams of ethylene chlorohydrine. Thenthere are added dropwise at 80 C. 76 grams of fi-ethoxy vinyl phosphonicacid dichloride and the temperature is kept for 1 further hour at 90 C.After Working up as usual there are obtained 60 grams of the new esterof B.P. 0.01 mm./ 87 C. Yield: 60% of the theoretical. Toxicity on ratsper osmium LD 25 mgJkg'.

By the same way but using instead of ethylene chlorohydrine theequirnolecular amount of propylene chlorohydrine there is obtained theester of the following formula 85 grams of sodium fluoride are suspendedin 200 millilitres of toluene. Thereto are added 41 grams of pinacolinealcohol. Then there are added dropwise at 80 C. 76 grams of ,B-ethoxyvinyl phosphonic acid dichloride. The temperature is kept for 1 furtherhour at 90 C. and the'mixture is worked up as usual. There are obtained82 grams of the new ester. Yield: 86% of the theoretical. The ester isdistillable under decomposition even in high vacuum. Toxicity on ratsper osmium LD 500 mg./kg.

We claim:

1. Phosphonic acid ester fluorides of the following general formula Fwherein R stands for lower alkyl radicals up to 4 carbon atoms and Rstands for a member selected from the group consisting of alkyl radicalsup to 6 carbon atoms and monochloro substitution products thereof.

2. The phosphonic acid ester fluoride of the following general formula F3. The phosphonic acid ester fluoride of the following general formula6. The phosphonic acid ester fluoride of the following general formula F7. The phosphonic acid ester fluoride of the following general formula F8. The phosphonic acid ester fluoride of the following general formula 0OCH: Il/ ciHlscH=CHP 6 9. The phosphonic acid ester fluoride of thefollowing general formula 10. The phosphonic acid ester fluoride of thefollowing general formula 11. A phosphonic acid fluoride of thefollowing general formula where R stands for lower alkyl radicals up to4 carbon atoms and R stands for a member selected from the groupconsisting of alkyl radicals up to 6 carbon atoms and monochlorosubstitution products thereof.

12. A phosphonic acid fluoride of the following general formula whereinR stands for lower alkyl radicals up to 4 carbon atoms and R stands fora member selected from the group consisting of alkyl radicals up to 6carbon atoms and monochloro substitution products thereof.

13. A phosphonic acid fluoride of the following general formula whereinR stands for lower alkyl radicals up to 4 carbon atoms and R stands fora member selected from the group consisting of alkyl radicals up to 6carbon atoms and monochloro substitution products thereof.

14. A phosphonic acid fluoride of the following general formula whereinR stands for lower alkyl radicals up to 4 carbon atoms and R stands fora member selected from the group consisting of alkyl radicals up to 6carbon atoms and monochloro substitution products thereof.

No references cited.

UNITED STATES PATENT OFFICE CERTIFICATION OF CORRECTION Patent No.2,962,517 November 29 l 1960 Hans-Joachim Tuppack et ale It ishherebycertified that error appears in the above numbered patent requiringcorrection and that the said Letters Patent should read as correctedbelow.

Column 3, lines 3 to 6, the formula should appear as shown below insteadof as in the patent:

s oc n column 4, lines 34 and 51, and column 5, line 2 for "osmium",each occurrence, read 05 Signed and sealed this 27th day of June 1961.

(SEAL) Attestz ERNESTWO SWIDER DAVID L, LADD Att'efsting OfficerCommissioner of Patents

1. PHOSPHONIC ACID ESTER FLUORIDES OF THE FOLLOWING GENERAL FORMULA